Stable blends of cationic water-in-oil emulsion polymers and cationic aqueous solution polymers

ABSTRACT

Novel, stable blends of cationic water-in-oil emulsion polymers with cationic polymers in aqueous solution are preparable through the use of stabilizing solvents and surfactants.

FIELD OF THE INVENTION

This invention relates to stable blends or combinations of cationicpolymers in inverse emulsion form with cationic polymers in aqueoussolution.

BACKGROUND OF THE INVENTION

Water-soluble polymers in water-in-oil (inverse) emulsion form, i.e.,water-soluble polymer/water as the discrete phase of the emulsion, andhydrocarbon solvent as the continuous phase of the emulsion, have foundgreat utility in water treatment and related industries. The utility ofthe inverse emulsions is in large measure due to their ability to supplyhigh concentrations of high molecular weight water-soluble polymers in"liquid", free-flowing form. As is well known to those skilled in theart, high molecular weight water-soluble polyelectrolytes are veryviscous in solution, and concentrations in water above about 1% areextremely viscous and difficult to pour, pump, etc.

These inverse emulsion products generally comprise approximately equalquantities of hydrocarbon, polymer and water (about 30% of each),together with hydrophobic surfactants for stabilization of the emulsionand hydrophilic surfactants for subsequent inversion into water for use.

In order for these inverse emulsions to be used for variousapplications, including water-treatment, they generally must beactivated by inversion of the emulsion, from a water-in-oil emulsion toan oil-in-water emulsion. This is generally done by diluting theemulsion with water. The self-inverting characteristics of the emulsionswhich contain the inverting surfactant thus allow the polymer to be"released" into the water, making the polymer available for use. By thesame token, the oil phase becomes the discontinuous phase, and what isobtained when the emulsion is diluted with water is a hazy solution ofthe polymer in water, the haziness being the emulsified oil.

The inversion is generally conducted with sufficient quantities of watersuch that the polymer will be approximately at use concentration,usually about one percent polymer on an active basis, or less. Thus, onegram of emulsion containing about 30% polymer will require about 33 g ofwater in order to achieve a one percent solution. As is well known inthe art, the polymers contained in the inverse emulsions are generallyof high molecular weight, usually greater than one million up to about20 million or more. For this reason, solutions, of these high molecularweight polymers become very viscous above about one percentconcentration in water, thus limiting their ability to be pumped, etc.Also for the aforementioned reasons, the inversion must be carefullyconducted so that localized regions of high polymer concentration areavoided. Thus, the emulsion is always added to the well stirred aqueousportion.

One consequence of the self-inverting characteristics of thewater-in-oil emulsions is that they are "unstable" in the presence ofwater. Thus, if a small amount of water is inadvertently introduced intothe emulsion, the emulsion will invert in the area where thecontaminating water is present. Since the polymer concentration in thelocalized area will tend to be very high, the inverted portion will havean extremely high viscosity, and may even be "gel" like. This results inan unusable portion of polymer which is also objectionable because itwill tend to clog transfer lines, pumps, and the like.

The contamination of these emulsions with water is a common occurrencein manufacturing plants, shipping, and in use location, and causes manyproblems in cleanup, filtration, and lost time. Such contamination canoccur through spills, rain falling into open drums and tank trucks, andthe like, and has resulted in increased surveillance on the part ofpersonnel to avoid the possibility of contamination. It is thus wellknown that inverse emulsions of water-soluble polymers are incompatiblewith significant quantities of water, with the obvious exception of thedilution of the emulsions with such great quantities of water that thepolymers will be at their practicable use concentrations (about 1% orless).

It is also known to those in the industry that combination treatments,in various applications, of these high molecular weight water-solublepolymers, in inverse emulsion form, with concentrated aqueous solutionsof lower molecular weight polymers can be very useful. Because of theheretofore perceived inability of those skilled in the art to be able tocombine the emulsions with the "destabilizing" aqueous solutions, thesecombinations treatments have always been utilized as dual treatments,i.e., the polymers would be added in separate streams, from separatedrums or tanks. In particular, many applications exist where highmolecular weight cationic polymers in inverse emulsion form are used incombination with lower molecular weight cationic polymers inconcentrated aqueous solution, via dual treatment systems.

SUMMARY OF THE INVENTION

The inventors of the instant invention have surprisingly found that highmolecular weight cationic polymers in inverse emulsion form can becombined with aqueous solutions of lower molecular weight cationicpolymers to form stable mixtures which are novel and useful. Thesemixtures comprise a wide range of useful compositions and ratios, whichhave heretofore been unknown and thought incapable of existing in stableform, i.e., without formation of gels, and with stable viscosities.These combinations are made possible through the use of certainstabilizing surfactants and solvents, to be described later herein. Thestabilizing solvents and surfactants are added in surprisingly smallamounts to provide the blends with acceptable stability.

Within certain narrow concentrations and ratios, the high molecularweight cationic polymers in inverse emulsion form can be combined withsmall amounts of the lower molecular weight cationic polymers in aqueoussolution without addition of stabilizing agents. Far more useful,however, and the essence of our invention, is the ability to combine theaforementioned cationic emulsion polymers with the aqueous cationicpolymers over a wide range of compositions and ratios through the use ofstabilizing solvents and surfactants. The use of these stabilizingcomponents allows the formulation of compositions for a great manyapplications in water and wastewater treatment.

DESCRIPTION OF THE PRIOR ART

Frisque, U.S. Pat. No. 3,806,485, assigned to Nalco Chemical Co.,discloses combinations of anionic vinyl addition polymers, in inverseemulsion form, with water soluble cationic polymers. The '485 patentdoes not contemplate, nor even suggest, that cationic vinyl additionpolymers in inverse emulsion form could be mixed with cationic watersoluble polymers. The '485 polymer mixtures are inherently unstable, andform highly water insoluble gels when inverted in water. The instantinvention produces stable mixtures of cationic polymers in inverseemulsion form with cationic polymers in aqueous solution. Furthermore,when the instant mixtures are "inverted" into water a completely solublemixture of polymers is the result. The '485 patent does not suggest inany way that stabilizing agents or solvents could be added to themixtures of anionic emulsion polymer and cationic aqueous polymer. The'485 patent goes so far as to suggest that "self-inverting" emulsions,i.e., emulsions which already contain the inverting surfactants, areunstable and must be carefully formulated or else the emulsion will bedestroyed (col. 5, lines 72-75; col. 6, lines 1-3). The instantinvention contemplates the use of self-inverting emulsions incombination with cationic polymers in aqueous solution, and providesmethods for stabilizing these mixtures. Thus, the '485 patent is notconsidered relevant to the instant invention.

Barron, U.S. Pat. No. 3,691,124, assigned to Dow Chemical Company,teaches the use of cationic polymers to stabilize inverse emulsions.Close examination of the teachings of this patent reveal that it is notrelevant to the instant invention. A key feature is that the '124polymers which are added to the inverse emulsion polymers are restrictedto oil-phase solubility and are added solely to impart additionalstability to the emulsions. They are not utilized as components of theactive polymer treatments. The '124 stabilizing polymers are restrictedto acrylate ester copolymers, and the cationicity is imparted solelythrough a tertiary amine functionality. No mention of the utility ofquaternary ammonium salts is made or suggested. The '124 stabilizingpolymers also appear to be limited to about 5 weight percent inquantity.

Anderson, et al., U.S. Pat. No. 3,826,771, disclose the use of higherconcentrations of water in the dispersed phase of the inverse emulsionto make the emulsions more stable. This patent is not pertinent to thepresent invention since '771 does not contemplate mixing aqueoussolutions of polymers with the inverse emulsions, and does notcontemplate the use of stabilizing solvents and surfactants.Furthermore, water concentration is not a key element to the presentinvention (except that very high concentrations of water can cause theproblems mentioned earlier, namely destabilization of the emulsion).

DETAILED DESCRIPTION OF THE INVENTION

The present inventors discovered that cationic, high molecular weight,water-soluble polymers in water-in-oil emulsion form unexpectedly can becombined with cationic polymers in aqueous solution to give stableblends. The stable blends are obtained through the use of stabilizingsurfactants and solvents, which can be added in surprisingly smallamounts and still provide stability to the mixtures of cationic inverseemulsion polymers and aqueous cationic polymers.

Further, a stable emulsion blend may be obtained without additionalsurfactants and solvents when the cationic emulsion polymer and thecationic polymer in aqueous solution are combined in a weight ratio offrom about 5 to about 95 percent.

The high molecular weight cationic emulsion polymers which are thesubject of the invention are well known to those practicing in the art.The polymers generally comprise acrylamide copolymers produced with avariety of cationic comonomers; e.g., ethylenically unsaturated cationicmonomers. The cationic monomers can be either amine containing monomersor quaternary ammonium salt containing monomers as depicted by thefollowing formulas: ##STR1## wherein R₁ in the above formula representshydrogen or lower alkyl (e.g., C₁ -C₃); R₂ and R₃ independentlyrepresent hydrogen or hydroxyl; R₄, R₅, and R₆ independently representlower alkyl (e.g., C₁ -C₃) or benzyl; A represents O or NH; y is 1-5;and X represents chloride or methosulfate.

Typical of the cationic monomers commonly copolymerized with acrylamideare: the aminoalkylacrylate esters and their quaternary ammonium salts(quaternization with such quaternizing agents as methyl chloride,dimethyl sulfate, benzyl chloride and the like); theamonialkylmethacrylate esters and their corresponding quaternaryammonium salts; the aminoalkylacrylamides and their correspondingquaternary ammonium salts; the aminoalkylmethacrylamides and theircorresponding quarternary ammonium salts; the diallyldialkylammoniumsalt monomers; the vinylbenzyltrialkylammonium salts; and the like.Non-limiting examples of the cationic monomers that can be used toprepare the cationic emulsion polymers in our invention are:diallyldimethylammonium chloride; diallyldiethylammonium chloride;acryloyloxyethyltrimethylammonium chloride;methacryloyloxyethyltrimethylammonium chloride;acryloyloxyethyltrimethylammonium methosulphate;methacryloyloxyethyltrimethylammonium methosulphate;acryloyloxyethyldiethylmethylammonium chloride;methacryloyloxyethyldiethylmethylammonium chloride;methacryloyloxyethyldiethylmethylammonium chloride; and,methacryloyloxyethyldiethylmethylammonium chloride. Mixtures of thecationic monomers together with acrylamide to prepare the cationicpolymers are also useful for our invention. The instant invention alsocontemplates homopolymers of the cationic monomers, as well ascopolymerization of mixtures of cationic monomers without acrylamide asuseful. The above description of useful cationic monomers in no waylimits the practice of our invention. Those skilled in the art will befamiliar with other cationic monomers which can be used to prepare thecationic, high molecular weight polymers useful in our invention.

The cationic polymers can have a wide range of charge densities, fromjust a few mole percent of cationic monomer up to 100 mole percent ofcationic monomer (homopolymers). The molecular weights of the cationicemulsion polymers are not critical to out invention, but can range froma few hundred thousand to several million. Those in the art recognizethat for many of the applications for which these polymers are useful,activity of the polymers will increase as the molecular weightsincrease.

Preparation of the cationic emulsion polymers is well known and isdescribed in the literature in detail. Typical procedures and methodscan be found, for example, in reissued U.S. Pat. No. 3,624,019, reissuedas Re. 28,474, herein incorporated by reference. It is important to notethat most commercially available inverse emulsion polymers availabletoday contain the inverting surfactant as part of the formulation, andare thus "self-inverting", and our invention prefers, but is not limitedto, the use of these self-inverting emulsion polymers.

The cationic aqueous polymers can be any cationic, water-soluble polymerwhich can be prepared in "substantial" concentration in water. By"substantial" is meant concentrations which are sufficiently high tomake preparation and shipping of the polymers in aqueous solutioneconomically practical. Thus, the concentrations of the aqueous cationicpolymers can be anywhere from about 10 weight percent to about 90 weightpercent, with concentrations from about 20 weight percent to about 75weight percent being preferred. The worker in the art will recognizethat in order for the water soluble polymers to meet the requirement ofconcentration, the molecular weights will tend to be lower than, but notlimited to, those of the cationic, high molecular weight polymers ininverse emulsion form. The polymers comprising the class of cationicpolymers in aqueous solution contemplated by our invention includes butis not limited to, both addition polymers, usually prepared by freeradical initiation, and the so-called condensation polymers, usuallyprepared without special initiators. Examples of the types of cationicpolymers in aqueous solution which are useful in accordance with theinvention include, but are not limited to: polydiallyldimethylammoniumsalts, including the chloride salt; polydiallyldiethylammonium salts,including the chloride salt; the polyquaternary ammonium salt polymersprepared from epihalohydrins and their precursors reacted with dialkylamines, with or without small amounts of amines with higherfunctionality, described in Panzer, et. al., in reissued U.S. Pat. No.28,807 and 28,808 (reissues of U.S. Pat. No. 3,738,945) hereinincorporated by reference; and the like. Descriptions of suitablecationic polymers can be found in the article on "Polyamines andPolyquaternary Ammonium Salts", in the Encyclopedia of Polymer Scienceand Engineering, Second Edition, John Wiley & Sons, New York, Volume 11,pages 489-507. It is to be understood that our invention is in no waylimited by the above descriptions of cationic polymers. Those skilled inthe art will recognize other cationic polymers which will be useful inthe practice of our invention. Mixtures of cationic aqueous polymers arealso contemplated by this invention.

The stabilizing surfactants comprise two types. The first encompassesthe hydrophobic, so-called low HLB surfactants which are documented inthe literature, and which are described in the Atlas HLB SurfactantSelector, with commercial versions listed in "McCutcheon's Emulsifiersand Surfactants", published by McCutcheon Division, Mc Publishing Co.,Glen Rock, N.J. These hydrophobic surfactants generally are soluble inhydrocarbons, and generally are insoluble in water. Those skilled in theart will recognize that these types of surfactants are those used as theemulsifying surfactants for the inverse emulsions. Typical of thesesurfactants, although not limiting, is sorbitan monooleate, which issold, in one version, as Span® 80 by ICI Americas, Inc.

The second type of stabilizing surfactants are the hydrophilic,generally water soluble surfactants. Surfactants of this type aredescribed in reissued U.S. Pat. No 28,474, herein incorporated byreference. Typical, although not limiting, of this class of surfactantsare the alkoxylated surfactants, in particular the nonylphenols, havingfrom 5-50 moles of ethoxylation. Preferred for our invention, althoughnot limiting, are the nonylphenols having 9-10 moles of ethoxylation.One version of this preferred surfactant is Surfonic® N-95, sold byTexaco Chemical Co.

It has been unexpectedly found that the combination ofstabilizing"emulsifying" and "inverting" surfactants can be used intotal amounts of as little as about 0.5% and still provide activity instabilizing the blend of cationic inverse emulsion polymer and cationicaqueous polymer. Since the surfactants used in preparing the inverseemulsions and making them self-inverting can amount to as much as about10% of the total weight of emulsion, it is to be recognized that theadditional surfactants used to stabilize the blend of polymerssurprisingly can represent a small fraction of the total amount ofsurfactants present. The maximum amounts of stabilizing surfactantscontemplated in our invention is about 10%. In general, the amount ofstabilizing surfactants is determined by the quantity of water presentin the cationic aqueous polymer, with more dilute solutions requiringhigher amounts of surfactants.

The stabilizing solvents used in accordance with the invention arehydrocarbon liquids and can include aliphatic, mixed aliphatic/aromatic,or aromatic solvents. Particularly useful solvents are the aliphaticsolvents, with the low odor, low aromatic paraffinic solvents preferred.Non-limiting examples of the preferred solvents are deodorized keroseneand the low odor, low aromatic solvent sold by Exxon as Low OdorParaffin Solvent (LOPS). Concentrations of stabilizing solvents fromabout 2% to about 20% of the total formulation are useful, with about 5to about 10% preferred. As with the stabilizing surfactants, morestabilizing solvent is needed as the water content of the cationicaqueous polymer increases.

The order of addition of ingredients for the formulation can becritical. It is preferred that the order of addition be as follows:cationic inverse emulsion polymer, stabilizing solvent, stabilizingsurfactants, cationic aqueous polymer. The aqueous cationic polymershould not be added first in any case, as this usually leads toinstability of the formulation. If the concentration of aqueous cationicpolymer is less than about 25% of the total, the aqueous polymer couldbe added to the emulsion polymer before the solvent/surfactants, butthis is not desirable. The order of addition of solvent/surfactants tothe emulsion is not critical, but preferred is solvent followed byhydrophobic surfactant followed by hydrophilic surfactant. The solventcould be added to the cationic emulsion polymer followed by the cationicaqueous polymer, and then the surfactants, except where the aqueousportion of the cationic aqueous polymer would constitute more than about25% of the total formulation. By the same token, the order of additioncould be cationic inverse emulsion polymer, solvent, hydrophobicsurfactant, cationic aqueous polymer, hydrophilic surfactant, butundesirable would be cationic inverse emulsion polymer, solvent,hydrophilic surfactant, cationic aqueous polymer, hydrophobicsurfactant. Another undesirable order of addition is cationic inverseemulsion polymer, surfactants, cationic aqueous polymer, solvent.

The invention is further illustrated by the following specific, butnon-limiting, examples.

In the following tables, the numbered polymers are identified as follows(all cationic inverse emulsion polymers are self-inverting, i.e., theycontain the hydrophilic, inverting surfactant as part of the product):

Polymer 1--Commercial cationic copolymer of acrylamide andacryloyloxyethyldiethylmethylammonium chloride, containing about 8 mole% of the cationic monomer, having a molecular weight in excess of onemillion, in inverse emulsion form.

Polymer 2--Commercial cationic copolymer of acrylamide andacryloyloxyethyldiethylmethylammonium chloride, containing about 40 mole% of the cationic monomer, having a molecular weight in excess of onemillion, in inverse emulsion form.

Polymer 3--Commercial cationic copolymer of acrylamide andmethacryloyloxyethyldiethylmethylammonium chloride, containing about 7.5mole % of the cationic monomer, having a molecular weight in excess ofone million, in inverse emulsion form.

Polymer 4--Commercial cationic copolymer of dimethylamine andepichlorohydrin, having a molecular weight of about 10,000, in 40%aqueous solution.

Polymer 5--Commercial cationic diallyldimethylammonium chloride polymer,having a molecular weight of about 500,000, in 18% aqueous solution.

All compositions are given in weight percents. The stability ratings areas follows:

1=stable: equivalent in stability to the "parent" emulsion after sixweeks accelerated aging tests, i.e., less than 10% separation, withreadily redispersed sludge, when stored at 40 degrees F., ambient, or122 degrees F. for six weeks. The formulation would also haveself-inversion characteristics equivalent to the parent emulsion.

2=unstable; shear sensitive; viscosity increases significantly withshear

3=unstable; product separation occurs rapidly

4=unstable; shear sensitive; viscosity increases significantly withshear; gelled particles observed

5=unstable; product gelled

6=unstable; shear sensitive; viscosity increases only slightly withshear

The order of addition for these examples is the preferred order ofaddition; namely, cationic inverse emulsion polymer, stabilizingsolvent, stabilizing surfactants, cationic aqueous polymer.

                  TABLE I                                                         ______________________________________                                                   Formulation #                                                                 1    2          3      4                                           ______________________________________                                        Polymer 1    46.52  43.84      46.92                                                                              50.0                                      Polymer 4    46.52  43.84      46.92                                                                              50.0                                      LOPS         5.36   10.72      5.36 --                                        Span 80      0.86   0.86       0.43 --                                        Surfonic N-95                                                                              0.74   0.74       0.37 --                                        Stability    1      3          2    2                                         ______________________________________                                    

It can be seen from Table I that equal weight blends of the cationicinverse emulsion polymer with the cationic aqueous polymer are unstablewithout added stabilizers (Formulation 4). For this combination ofpolymers, it was found that combinations of stabilizing surfactantstotaling about 0.8% did not provide adequate stability, whereas levelsof combined stabilizing surfactants of about 1.6% provided goodstability (Formulation 1 vs. Formulation 3). In addition, for thiscombination of polymers, too high a level of stabilizing solvent gave anunstable formulation, whereas lower levels of stabilizing solventprovided good stability (Formulation 1 vs. Formulation 3).

                  TABLE II                                                        ______________________________________                                               Formulation #                                                                 5     6       7       8     9     10                                   ______________________________________                                        Polymer 2                                                                              46.92   49.5    50.0  49.5  49.5  47.1                               Polymer 4                                                                              46.92   49.5    50.0  49.5  49.5  47.1                               LOPS     5.36    --      --     5.0  --    5.36                               Span 80  0.43     1.0    --    --    --    0.44                               Surfonic N-95                                                                          0.37    --      --    --     1.0  --                                 Stability                                                                              1       5       4     2     5     6                                  ______________________________________                                    

For a different combination of cationic polymers, illustrated in TableII, it can again be seen that equal weight blends of the two polymersare unstable (Formulation 7), whereas with the stabilizing solvent andsurfactants, an acceptable blend can be formulated (Formulation 5 vs.Formulation 7). It is also illustrated that the solvent or individualsurfactants alone do not impart acceptable stability to the blends(Formulations 6, 8, and 9). Formulation 10, prepared without theinverting surfactant, was somewhat more stable than the formulationshaving a stability rating of "2", and demonstrates that, although theinverting surfactant is added primarily to aid in polymer inversion, itstill contributes a minor role to blend stabilization, and thus allthree stabilizing components are necessary for optimum product handlingcharacteristics.

                  TABLE III                                                       ______________________________________                                               Formulation #                                                                 11    12      13      14    15    16                                   ______________________________________                                        Polymer 2                                                                              45.0    46.92   46.0  44.20 20.45 25.0                               Polymer 5                                                                              45.0    46.92   46.0  44.20 61.35 75.0                               LOPS     8.4     5.36    5.7   10.0  16.0  --                                 Span 80  0.86    0.43    1.2   0.86  1.2   --                                 Surfonic N-95                                                                          0.74    0.37    1.1   0.74  1.0   --                                 Stability                                                                              1       2       2     3     1     5                                  ______________________________________                                    

For yet another combination of cationic inverse emulsion polymer andcationic aqueous polymer, it can be seen from Table III that an optimumlevel of stabilizing solvent (Formulation 11 vs. Formulation 14) and anoptimum combination of stabilizing solvent and stabilizing surfactants(Formula 11 vs. Formulations 12 and 13) are required to prepare a stableformulation. It is also demonstrated in Table III that higher ratios ofthe cationic aqueous polymer in the blend in general require higherlevels of stabilizing solvent for stability (Formulation 15 vs.Formulation 11), and that other ratios of the two polymeric componentsare unstable without the addition of the stabilizing solvent andsurfactants (Formulation 16 vs. Formulation 15).

                  TABLE IV                                                        ______________________________________                                                    Formulation #                                                                 17                                                                ______________________________________                                        Polymer 3     67.41                                                           Polymer 4     14.44                                                           Polymer 5     14.44                                                           LOPS          3.20                                                            Span 80       0.26                                                            Surfonic N-95 0.22                                                            Stability     1                                                               ______________________________________                                    

Table IV illustrates yet another stable combination of cationic inverseemulsion polymer, in this case with a mixture of two cationic aqueouspolymers.

Those skilled in the art will recognize the many applications in whichthese combinations will find utility. Generally the compositions of theinvention are used in water treatment particularly for the separation ofsuspended solids (organic or inorganic), emulsified materials, colloids,make-up, and the like from water. These include, but are not limited to,wastewater treatment applications, influent water clarification,secondary water clarification, oily water waste treatment, papermaking(e.g., fiber retention), protein recovery, emulsion breaking, sludgedewatering, upflow filter clarification, and the like. The polymercombinations of the invention may be used effectively on a product basisat dosages of 0.5 to 100 ppm and preferably 5 to 50 ppm of the systemtreated. The dosage, of course, is dependent upon the severity of theproblem.

Those skilled in the art will also recognize that these materials canalso be used in conjunction with other products, such as in water andwastewater applications, with other coagulating agents such as alum,ferric salts, clays, zeolites, activated carbon, and the like.

Field Trial

In order to establish the efficacy of a polymeric blend as provided bythe instant invention as compared to the feed of the polymeric materialsindependently, a product in accordance with the invention was used at aNew Hampshire paper facility which required waste sludge dewatering.Initially, separate feeds of an emulsion cationic polymer (Polymer 2described earlier herein) and cationic polymer in solution (Polymer 4described earlier herein) were used at separate feed points. Bestresults using the two feed system were achieved with a 70% feed ofPolymer 2 and a 30% Polymer 4 feed.

The blended product utilized in accordance with the present inventioncomprised a 50/50 blend of Polymer 2 and Polymer 4 with the specificformulation being represented as Formulation 5 of instant specification.

Results utilizing the blended product similar to Formulation 5 of theinstant specification were excellent, especially considering that theblended products' ratios were different and feed was at only one point.The blended product (Formulation 5) was fed through Polyblend unit withno aging.

The plant personnel were very impressed for several reasons: namely (1)one product feed, (2) no aging of the product required, (3) one feedpoint, and (4) the results achieved were just as good as the two feedapproach and cost competitive, avoiding the use of handling differentcontainers and the disposing of such. The blended product (Formulation5) had been made several months prior to use and when used did notrequire any drum agitation. The product held as a very stable emulsionand as good as any emulsion polymer handled to date by the individualconducting the trial.

Relative to the instantly claimed invention and in the inventors'estimation quite important is a different concept of producingcombination polymeric products. In accordance with this particularconcept, the first step would involve the emulsification of the liquidpolymer product, which requires the addition of oil and surfactants tothe most concentrated form of the liquid polymer that was available. Theemulsification would be achieved via intense mechanical agitation, suchas produced in the laboratory with a Ross Emulsifier or a high-speedimpeller. The recommended oil and surfactants are those which aretypical of the kind used to make emulsion polymer products such as Betz®Polymer 1154L, and are preferably identical to those in the commercialemulsion product. Specific examples of oils and surfactants are wellknown, having been delineated in the literature. The emulsified liquidpolymer material would only have to be stable for a brief time period toallow it to be blended with the emulsion polymer product.

The second step entails blending together of the above emulsified liquidpolymer product with the commercial emulsion polymer product. This wouldagain require intense mechanical agitation. Emulsification of the liquidpolymer would assure that the hydrophobic and hydrophilic componentswere compatible when it was blended with the commercial emulsion polymerproduct. That is, the oil phase would remain the predominant, continuousphase, with the aqueous phase (which contains the polymers) disperseduniformly throughout.

Mixing the liquid polymer product directly into the emulsion product didnot result in stable blends. Adding additional oil and surfactants tothe emulsion product, and then mixing in the liquid polymer, was analternative sequence to achieve similar (but not identical) physicalconditions to those embodied in this concept. That is, the sequence ofadditions may have an effect on the stability of the final blend.

Although the concept has been stated specifically for the case ofcationic polymers, there is every reason to believe that stable blendsof anionic and/or nonionic liquid and emulsion polymers (e.g., a liquidpolyacrylate, polymethacrylate, or acrylicacid/1-allyloxy-2-hydroxypropane-3-sulfonic acid, and emulsionpolyacrylamide or polyacrylic acid) could be made by the same method.

Having described our invention what is claimed is:
 1. Composition ofmatter comprising a blend of a cationic polymer in water-in-oil emulsionform with at least one different cationic polymer in aqueous solutionwherein said cationic polymer in water-in-oil emulsion form and saiddifferent cationic polymer in aqueous solution are combined in a weightratio from about 5 to about 95 percent and said blend does not form gelsand maintains stable viscosity.
 2. Composition of matter comprising astable combination of cationic polymer in water-in-oil emulsion form, adifferent cationic polymer in aqueous solution, hydrocarbon solvent, andhydrophobic and hydrophilic surfactants wherein said combination doesnot form gels and maintains stable viscosity.
 3. Composition accordingto claim 1, wherein said cationic polymer in water-in-oil emulsion formis a homopolymer of an ethylenically unsaturated cationic monomer, or acopolymer of said cationic monomer with acrylamide or methacrylamide. 4.Composition according to claim 3, wherein said ethylenically unsaturatedcationic monomer has the formula: ##STR2## wherein R₁ in the aboveformula represents hydrogen or lower alkyl; R₂ and R₃ independentlyrepresent hydrogen or hydroxyl; R₄, R₅, and R₆ independently representlower alkyl or benzyl; A represents 0 or NH: y is 1-5; and X representschloride or methosulfate.
 5. Composition according to claim 4, whereinsaid cationic monomer is acryloyloxyethyltrimethylammonium chloride. 6.Composition according to claim 4, wherein said cationic monomer isacryloyloxyethyltrimethylammonium methosulfate.
 7. Composition accordingto claim 4, wherein said cationic monomer isacryloyloxyethyltrimethylammonium chloride.
 8. Composition according toclaim 4, wherein said cationic monomer isacryloyloxyethyltrimethylammonium methosulfate.
 9. Composition accordingto claim 4, wherein said cationic monomer ismethacryloyloxyethyltrimethylammonium chloride.
 10. Compositionaccording to claim 4, wherein said cationic monomer ismethacryloyloxyethyltrimethylammonium methosulfate.
 11. Compositionaccording to claim 4, wherein said cationic monomer ismethacryloyloxyethyltrimethylammonium chloride
 12. Composition accordingto claim 4, wherein said cationic monomer is diallyldimethylammoniumchloride.
 13. Composition according to claim 4, wherein saidethylenically unsaturated cationic monomer is a mixture of ethylenicallyunsaturated cationic monomers.
 14. Composition according to claim 1,wherein said cationic polymer in aqueous solution is a copolymer of anepihalohydrin with a dialkylamine.
 15. Composition according to claim14, wherein said cationic polymer in aqueous solution is a copolymer ofepichlorohydrin and dimethylamine.
 16. Composition according to claim14, wherein said cationic polymer in aqueous solution ispolydiallyldimethylammonium chloride.
 17. Composition according to claim14, wherein said cationic polymer in aqueous solution is a terpolymer ofepichlorohydrin, dimethylamine, and ethylenediamine.
 18. Compositionaccording to claim 3, wherein said copolymer of acrylamide ormethacrylamide with said ethylenically unsaturated cationic monomercontains about 0.5 to about 100 mol % of said ethylenically unsaturatedcationic monomer.
 19. Composition according to claim 18, wherein saidmole ratio of ethylenically unsaturated cationic monomer to acrylamideor methacrylamide is about 5 to about 75 mole percent.
 20. Compositionaccording to claim 18, wherein said copolymer is a copolymer ofacrylamide and said ethylenically unsaturated cationic monomer with amole ratio of ethylenically unsaturated cationic monomer to acrylamideof about 5 to about 15 mole percent.
 21. Composition according to claim18, wherein said copolymer is a copolymer of acrylamide with saidethylenically unsaturated cationic monomer with a mole ratio of saidethylenically unsaturated monomer to acrylamide of about 30 to about 60mole percent.
 22. Composition according to claim 20, wherein saidcopolymer is a copolymer of acrylamide andacryloyloxyethyltrimethylammonium chloride having a mole ratio ofacryloyloxyethyltrimethylammonium chloride to acrylamide of about 7 toabout 10 mole percent.
 23. Composition according to claim 21, whereinsaid copolymer is a copolymer of acrylamide andacryloyloxyethyltrimethylammonium chloride having a mole ratio ofacryloyloxyethyltrimethylammonium chloride to acrylamide of about 40mole percent.
 24. Composition according to claim 20, wherein saidcopolymer is a copolymer of acrylamide andmethacryloyloxyethyltrimethylammonium chloride having a mole ratio ofmethacryloyloxyethyltrimethylammonium chloride to acrylamide of about 6to about 9 mole percent.
 25. Composition according to claim 20, whereinsaid copolymer is a copolymer of acrylamide andmethacryloyloxyethyltrimethylammonium chloride having a mole ratio ofmethacryloyloxyethyltrimethylammonium chloride to acrylamide of about 40mole percent.
 26. Composition according to claim 20, wherein saidcopolymer is a copolymer of acrylamide andacryloyloxyethyltrimethylammonium methosulfate having a mole ratio ofacryloyloxyethyltrimethylammonium methosulfate to acrylamide of about 7to about 10 mole percent.
 27. Composition according to claim 20, whereinsaid copolymer is a copolymer of acrylamide andacryloyloxyethyltrimethylammonium methosulfate having a mole ratio ofacryloyloxyethyltrimethylammonium methosulfate to acrylamide of about 40mole percent.
 28. Composition according to claim 20, wherein saidcopolymer is a copolymer of acrylamide andmethacryloyloxyethyltrimethylammonium methosulfate having a mole ratioof methacryloyloxyethyltrimethylammonium methosulfate to acrylamide ofabout 6 to about 9 mole percent.
 29. Composition according to claim 20,wherein said copolymer is a copolymer ofmethacryloyloxyethyltrimethylammonium methosulfate having a mole ratioof methacryloyloxyethyltrimethylammonium methosulfate to acrylamide ofabout 40 mole percent.
 30. Composition according to claim 1, whereinsaid cationic polymer in water-in-oil emulsion form has a molecularweight of about 500,000 to about 100,000,000.
 31. Composition accordingto claim 1, wherein said cationic polymer in aqueous solution has amolecular weight of from about 5,000 to about 5,000,000.
 32. Compositionaccording to claim 2, wherein aid solvent is comprised of a hydrocarbonor a mixture of hydrocarbons.
 33. Composition according to claim 32,wherein said hydrocarbon is an aliphatic hydrocarbon liquid. 34.Composition according to claim 32, wherein said hydrocarbon is a blendof aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds.35. Composition according to claim 33, wherein said aliphatichydrocarbon liquid is an isoparaffinic solvent.
 36. Compositionaccording to claim 33, wherein said aliphatic hydrocarbon liquid is adeodorized kerosene.
 37. Composition according to claim 33, wherein saidaliphatic hydrocarbon liquid is a low odor paraffinic solvent. 38.Composition according to claim 33, wherein said hydrocarbon is anaromatic hydrocarbon liquid.
 39. Composition according to claim 2,wherein said surfactants are comprised of hydrophobic surfactants andhydrophilic surfactants.
 40. Composition according to claim 39, whereinsaid hydrophobic surfactant is oil soluble.
 41. Composition according toclaim 40, wherein said hydrophobic surfactant is sorbitan monooleate.42. Composition according to claim 39, wherein said hydrophilicsurfactant is water soluble.
 43. Composition according to claim 42,wherein said surfactant is an alkoxylated alkyl phenol.
 44. Compositionaccording to claim 43, wherein said surfactant is an ethoxylated alkylphenol.
 45. Composition according to claim 43, wherein said surfactantis an ethoxylated nonyl phenol.
 46. Composition according to claim 43,wherein said surfactant is an ethoxylated octyl phenol.
 47. Compositionaccording to claim 44, wherein said surfactant is an ethoxylated alkylphenol having from about 5 to about 50 moles of ethoxylation. 48.Composition according to claim 44, wherein said surfactant is anethoxylated alkyl phenol having from about 5 to about 20 moles ofethoxylation.
 49. Composition according to claim 44, wherein saidsurfactant is an ethoxylated alkyl phenol having from about 8 to about12 moles of ethoxylation.
 50. Composition according to claim 45, whereinsaid surfactant is an ethoxylated nonyl phenol having from about ≡toabout 50 moles of ethoxylation.
 51. Composition according to claim 45,wherein said surfactant is an ethoxylated nonyl phenol having from about5 to about 20 moles of ethoxylation.
 52. Composition according to claim45, wherein said surfactant is an ethoxylated nonyl phenol having fromabout 8 to about 12 moles of ethoxylation.
 53. Composition according toclaim 32, wherein said solvent is added to the blend of cationicwater-in-oil emulsion polymer and cationic aqueous polymer at about 1 toabout 20 weight percent.
 54. Composition according to claim 39, whereinsaid surfactants are added to the blend of cationic water-in-oilemulsion polymer and cationic aqueous polymer at about 0.1 to about 20weight percent.
 55. Composition according to claim 2, wherein thepreferred order of addition is cationic polymer in water-in-oil form,hydrocarbon solvent, hydrophobic and hydrophilic surfactants, cationicpolymer in aqueous solution.
 56. Composition of matter comprising acombination of cationic polymer in water-in-oil emulsion form, cationicpolymer in aqueous solution, hydrocarbon solvent and hydrophobic andhydrophilic surfactants wherein said cationic polymer in water-in-oilemulsion form ranges from about 20 to about 90 weight percent; saidcationic aqueous polymer ranges from about 10 to about 90 weightpercent; said hydrocarbon solvent ranges from about 2 to about 20 weightpercent and said hydrophobic and hydrophilic surfactants range fromabout 0.5 to about 10.0 weight percent.